Preparation of mixed cellulose ethers



PatentedFeb. 25, 1941 PREPARATION or man CELLULOSE 1 arms Floyd 0. Peterson and Arthur J. Bitty, Midland, Mich, to The Dow Chemical Compony, Midland, Micin, a corporation or Michi- No Drawing.

Application January 2a, 1939 Serial 170.253,!!!

1 Claim. (01. 260-231) r This invention relates to a process for the preparation of mixed ethers ofcelluiose and especially to such a process carried out-ina medium comprising anhydrous liquid ammonia.

In a co-pending application Serial No. 187,655, filed January 29, 1938 now ,U. 8. Patent No. 2,157,083, issued May 2,1939, of which the present application is a continuation-impart,there is disclosed a new method for thepreparation oi cel- 1o lulose ethers. The said new method comprises reacting substantially anhydrous cellulose with an alkali metal in a medium comprising anhydrous liquid ammonia and.in the presence of a liquid hydrocarbon, such as toluene. whichisinert to the cellulose and liquid ammonia and substantially inert to the action of alkalimetal, thereby to produce an alkali-cellulosate. The said ce1lu-. losate is then reacted in a liquid ammonia medium with an etherifyins agent, such, for example,

as an alkyl or aralkyl halide or sulphate. In the said co-pending application Serial No. 187,655, there is described a method of making mixed cellulose ethers by reacting an alkali cellulosate with one etherii'ying agent, separating the so-formed ether product, reacting the said product with further quantities of alkali metal in liquid ammonia medium to produce an alkali-metal salt of a cellulose ether, and then reactingthe said salt with a second etherif ying agent to produce a' mixed .ether product. While such atwo-step etheriilca- I tion will produce mixed cellulose ethers. we have found a more convenient method whereby such ethers may be produced in a single etheriflcation step, employing a mixture of etherii'ying agents.

According to the invention, substantially anhydrous cellulose is suspended in anhydrous liquid ammonia and converted to an alkali cellulosate suitably by the method of the aforesaid copending application Serial No. 187,655. Another 40 method whereby alkali metal cellulosate maybe prepared is disclosed in our co-pending application Serial No. 187,654, flied January 29, 1938 now U. 8. Patent No. 2,145,273, issued January 31, 1939. The latter method diil'ers from the former in that it employs an. alkali amide rather than free alkali metal to react upon the cellulose. Regardless of the manner in which the alkali cellulosate is prepared, it is not isolated from the reaction "mixture nor is 'it entirely freed from ammonia. While still containing at least enough ammonia to completely moisten the cellulosate, it is treated with the etherifying mixture which may comprise two or more etheriiying agents of the type customarily employed in the preparation of so cellulose ethers according to the older methods.

ple, the nitro, nitroso. amino, or other groups I etheriflcation reaction,

Such etherifying agents include the alkylhalides I such as ethylchloride, methyl bromide, methyl iodide, ethyl bromide, n-propyl chloride, n-butyl chloride, diethyl sulphate,-dimethyl sulphate, and v the like, aralkyl halides such as benzyl chloride, -5 benzyl bromide, phenyl ethyl chloride, phenyl ethyl bromide, and the like, ethylene oxide, epichlorhydrin, etc. There may be similarly employed substitution products of the etheriiying agents previously named containing, for exam- 10 substantially inert to ammoniaiand to the alkali metals at reaction temperature. In addition to the etherliying agents, there may also be present in the reaction vessel a liquid aromatic hydrocan 15 bon to serve as a dispersion agent or solvent for the cellulose ether. a

The amount of mixed etheriiyins ents employed may vary from 1 to 10, and ordinarily is about 6 equivalent weights per atom of alkali 20 metal. After the mixture of etherifying agents has been added to the alkali cellulosate, the mixture is allowed to stand, suitably with occasional agitation, at a-temperature between 'C'. and

-+25 0., under the corresponding vapor pressure 25 or ammonia, until the etheriilcation reaction is, complete. This ordinarily requlresdrom 3 to 20 hours or more (occasionally as much as'lll hours) depending upon the etheriiying agents employed, thetemperatureot the reaction, and the number 80 of atoms of alkali metal substituted in the cellulose molecule. We prefer to carry out the etheriflcation reaction while the liquid ammonia is being allowed to volatilize slowly away from.

the reaction mixture. I

Owing to the low temperature employed in the side reactions between ammonia or sodium and the etherifying agents are reduced to a minimum. When the etherlfy- 'ing agent employed is a mixture including methyl bromide or ethyl bromide, no appreciable amounts of ethyl amine; methyl amine, ethane, or ethylene are. detected in the gases escaping from-the reaction mixture.

After etherliication is complete and the amd5 monia has escaped from the reaction vessel, the mixture having in the meantime attained room temperature, the cellulose ether may be recovered according to any oi several methods. One satisiactoryprocedure is to discharge the reaction 50 mixture into boiling water while the mixture is still slightly alkaline, thus flashing ofl unreacted etheriiying agents (if these materials have boiling points below that elf-water), as well asvolatilizingany small amounts of amine which may I have been formed as a by-product, and steam distilling from the mixture any hydrocarbon which may have been employed as a suspension agent or solvent throughout the reaction. Other methods of recovery of the mixed cellulose ethers will be apparent to those skilled in the art.

Various methods of carrying out our invention may be illustrated by the following examples:

Example 1 ence of 500 parts of toluene which serves during this stage of the reaction as a catalyst and during the subsequent etherification as a dispersion medium. When the reaction was complete, as evidenced by the disappearance of the characteristic blue color of sodium invliquid ammonia, the ammonia was distilled until only about 200 parts of anhydrous ammonia remained in the reaction vessel. A mixture of etherifying agents consisting of 250 parts (2 moles) of benzyl chloride and 50 parts (1 mole) of methyl chloridedissolved in 1500 parts of toluene was added to the alkali cellulosate. The entire mixture was agitated for a few hours at a temperature below -33 C. When the etheriflcation reaction was substantially complete, the remainingliquid ammonia was distilled-from the mixture and the toluene suspension was poured into boiling water. The toluene was steam distilled from the mixture and the benzyl methyl cellulose was recovered as a light-colored solid. Analysis of the product showed it to contain approximately 1.5 benzyl groups per cellulose unit and approximately 1 methyl group.

Example 2 was then warmed up to allow the ammonia. to

distill therefrom completely. The lorol" ethyl cellulose was extracted from the crude product with petroleum ether, taken up in a solvent conmethanol, by volume, filtered, and the clear solution slowly mixed with a relatively large volis used here in the manner originally employed by Briscoe, Journal of the Society of Dyers and 'Colourists, 48, page 129 (1932), to define the mixture of alcohols produced from coconut oil by catalytic hydrogenation, and the mixture of alkyl halides corresponding thereto.

A variety of mixed ethers of cellulose were prepared in like manner, employing mixtures of etherifying agents of the various classes hereinbeiore suggested. The method has the advantage of producing mixed cellulose ethers in a single stage etheriflcation, in an anhydrous medium, under conditions of temperature and pressure such that all of the reacted etherifying agents enter into combination with the cellulose.

Excess etherifying agent which does not react with the cellulosate, is recoverable unchanged.

Other mode of applying the principle of our invention may be employed instead of those explained, change being made as regards the method and material herein disclosed, provided the step or reactants stated by any of the following claims, or the equivalent of such stated step or reactants, be employed.

We therefo e particularly point out and distinctly claim as our invention:

The single stage etheriflcation method which comprises reacting an alkali metal cellulosate containing approximately 3 atoms of alkali metal per mole of cellulose, in a medium of liquid ammonia and in contact with toluene, with a mixture of etherifying agents consisting of about 2 moles of benzyl chloride and about 1 mole of methyl chloride, at a temperature below about 33 C., until reaction is substantially complete, thereafter removing the remaining ammonia from the reaction mixture, and recovering the soformed benzyl methyl cellulose containing approximately 1.5 benzyl groups and approximately 1 methyl group per cellulose unit from the residual toluene medium.

; FLOYD C. PETERSON.

ARTHUR J. BARRY.

,sisting of 67 parts of benzene and 33 parts of 

